JPS6127414B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a pyridone-based azo dye. Specifically, the object of the present invention is to solve the general formula [] (wherein, It represents an aminosulfonyl group, an alkylsulfonyloxy group, an alkenylsulfonyloxy group, an arylsulfonyloxy group, an alkylaminosulfonyloxy group, an alkenylaminosulfonyloxy group, an arylaminosulfonyloxy group, a cycloalkylaminocarbonyl group or an alkylthiocarbonyl group,

[Formula] represents a benzene nucleus optionally substituted with a chlorine atom, a bromine atom, or a lower alkyl group, and R ¹ is an alkyl group having 1 to 12 carbon atoms, a hydroxy lower alkyl group, a lower alkoxy lower alkyl group , lower alkoxy lower alkoxy lower alkyl group, lower alkoxycarbonyl lower alkyl group, acyloxy lower alkyl group, aryloxy lower alkyl group, cyano lower alkyl group, lower alkylamino lower alkyl group, halogeno lower alkyl group, cycloalkyl group, aralkyl group , represents a phenyl group which may have a substituent or an alkenyl group having 2 to 4 carbon atoms, and the lower alkyl and alkoxy mentioned above are all alkyl and alkoxy having 1 to 6 carbon atoms. ) The purpose of this invention is to provide a method for producing a novel pyridone-based azo dye represented by the general formula [] (wherein, X and

[Formula] has the same meaning as in the general formula [] shown above. ) A compound represented by the general formula [] D-SO ₃ R ¹ ...... [] (wherein, D represents an optionally substituted phenyl group, and R ¹ is a compound represented by the general formula []). ) has the ^same meaning as in the general formula [ ^] Achieved by reacting with a compound represented by _the following formula ₍ in which R ² represents ^a lower alkyl group): be done. To explain the present invention in detail, in the compound represented by the above general formula [], which is one of the raw materials for the method of the present invention, X includes a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butyroxycarbonyl group. , cyanomethyloxycarbonyl group, hydroxyethoxycarbonyl group, methoxyethoxycarbonyl group, methoxypropoxycarbonyl group, ethoxymethoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, furfuryloxycarbonyl group , alkoxycarbonyl groups such as morpholinomethoxycarbonyl group; alkenyloxycarbonyl groups such as allyloxycarbonyl group, methylallyloxycarbonyl group, cinnamyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group, diethylaminocarbonyl group, di-
Alkylaminocarbonyl groups such as n-butylaminocarbonyl group, n-hexylaminocarbonyl group, tetrahydrofurfurylaminocarbonyl group, furfurylaminocarbonyl group, morpholinocarbonyl group; allylaminocarbonyl group, diallylaminocarbonyl group, cinnamylamino group Alkenylaminocarbonyl groups such as carbonyl groups; arylaminocarbonyl groups such as phenylaminocarbonyl groups and tolylaminocarbonyl groups; methylaminosulfonyl groups, n-butylaminosulfonyl groups, diethylaminosulfonyl groups, 2-ethylhexylaminosulfonyl groups, -Alkylaminosulfonyl groups such as n-butylaminosulfonyl group, tetrahydrofurfurylaminosulfonyl group, furfurylaminosulfonyl group, and morpholinoaminosulfonyl group; alkenyl groups such as allylaminosulfonyl group, diallylaminosulfonyl group, and cinnamylaminosulfonyl group Aminosulfonyl group; Arylaminosulfonyl group such as phenylaminosulfonyl group and tolylaminosulfonyl group; Alkylsulfonyloxy group such as methylsulfonyloxy group, n-propylsulfonyloxy group, n-octylsulfonyloxy group, and methoxyethylsulfonyloxy group Groups: Alkenylsulfonyloxy groups such as allylsulfonyloxy groups and cinnamylsulfonyloxy groups; Arylsulfonyloxy groups such as phenylsulfonyloxy groups, tolylsulfonyloxy groups, chlorophenylsulfonyloxy groups, and phenoxyphenylsulfonyloxy groups ; Alkylaminosulfonyloxy groups such as methylaminosulfonyloxy group, diethylaminosulfonyloxy group, n-butylaminosulfonyloxy group; Alkenylaminosulfonyl such as allylaminosulfonyloxy group, diallylaminosulfonyloxy group, cinnamylaminosulfonyloxy group Oxy group; arylaminosulfonyloxy group such as phenylaminosulfonyloxy group, tolylaminosulfonyloxy group, chlorophenylaminosulfonyloxy group; cycloalkylaminocarbonyl group such as cyclohexylaminocarbonyl group, cyclopentylaminocarbonyl group; ethylthio carbonyl group, n-butylthiocarbonyl group, methoxyethylthiocarbonyl group, methoxyethoxyethylthiocarbonyl group,
Substituted or unsubstituted alkylthiocarbonyl groups such as methoxycarbonylmethylthiocarbonyl groups;
Examples include arylthiocarbonyl groups such as phenylthiocarbonyl group and chlorophenylthiocarbonyl group.

Substituents of the benzene nucleus represented by [Formula] include chlorine atom; bromine atom; methyl group, ethyl group,
Examples include lower alkyl groups such as butyl group and isopropyl group. In addition, as for the sulfonic acid esters represented by the general formula [], specifically, D is a phenyl group or a substituted phenyl group such as p-tolyl group, and R ¹ is a methyl group, an ethyl group, a 2-
propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, sec-octyl group, tert-
Alkyl groups having 1 to 12 carbon atoms such as octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, 2-dodecyl group; hydroxyethyl group, hydroxypropyl group, etc. Hydroxy lower alkyl group; lower alkoxy lower alkyl group such as methoxyethyl group, methoxypropyl group, ethoxypropyl group; lower alkoxy lower alkoxy lower alkyl group such as methoxyethoxyethyl group, ethoxyethoxyethyl group; methoxycarbonylethyl group, ethoxycarbonyl Lower alkoxycarbonyl lower alkyl groups such as methyl group; Acyloxy lower alkyl groups such as acetyloxyethyl group and benzoyloxyethyl group;
phenoxyethyl group, tolyloxyethyl group,
Aryloxy lower alkyl groups such as methoxyphenoxyethyl group; cyano lower alkyl groups such as cyanomethyl group and cyanoethyl group; methylaminoethyl group, ethylaminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, morpholinomethyl group, etc. lower alkylamino lower alkyl group;
Halogeno lower alkyl groups such as chloroethyl group and bromoethyl group; cycloalkyl groups such as cyclohexyl group; aralkyl groups such as benzyl group, methylbenzyl group, phenethyl group, chlorophenethyl group;
Phenyl group; Phenyl group having a substituent such as chlorophenyl group, methoxyphenyl group, tolyl group; Alkenyl group having 2 to 4 carbon atoms such as allyl group, 2-methylallyl group, 3-methylallyl group, etc. . In addition, in the alkyl halides represented by the general formula [], examples of the halogen atom represented by Z include chlorine atom, bromine atom, and iodine atom, and specific examples of the halides include methyl bromide and iodide. Ethyl, ethyl bromide, n-propyl bromide, n-butyl iodide, n-butyl bromide, 2-ethylhexyl bromide, n-octyl bromide, n-hexyl iodide, bromide -Cyclohexyl, ethoxyethyl bromide, benzyl chloride, phenethyl bromide, phenoxyethyl chloride, cyanoethyl bromide, and the like. Further, specific examples of the di-lower alkyl sulfuric acid represented by the general formula [] include dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, di-n-butyl sulfate, and the like. Pyridone azo compounds represented by the general formula [] are produced by diazotizing substituted anilines in a conventional manner and
It can be obtained by coupling with cyano-4-methyl-6-hydroxy-2-pyridone or an alkali metal salt thereof such as sodium salt or potassium salt. In the method of the present invention, the compound represented by the general formula
- Pyridine, N-alkylpyrrolidones such as methylpyrrolidone, ketones such as acetone, alcohols such as methanol, etc.
In the presence of an organic or inorganic base such as piperidine, sodium carbonate, potassium carbonate, magnesium oxide or sodium hydroxide, sulfonic acid esters of formula [], alkyl halides of formula [] or alkyl halides of formula [] By heating with the dialkyl sulfuric acid represented by the formula at 30 to 200°C, the dye represented by the general formula [] can be obtained with good purity and good yield. Particularly, the method of the present invention can obtain favorable effects in terms of yield and purity when R in the general formula [] is a long-chain alkyl group having 5 to 12 carbon atoms. The compound represented by the above general formula [] obtained by the present invention is suitable for dyeing various synthetic fiber materials, particularly polyester fibers. In addition, polyacrylonitrile fibers, triacetate fibers,
Synthetic fibers made of synthetic or semi-synthetic polymeric substances such as diacetate fibers and polyurethane fibers can be dyed in bright greenish-yellow tones with good fastness. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 3.1g of compound represented by the following formula A mixture of 2.0 g of sodium carbonate, 5.79 g of p-toluenesulfonic acid-n-octyl ester and 20 ml of N-methylpyrrolidone was heated to 100°C and
It was kept warm for hours. Then, after cooling to room temperature, add 100% water.
The precipitated crystals were collected, washed, and dried to obtain 4.1 g of a compound represented by the following structural formula. When polyester fibers were dyed at high temperature (130°C) using this dye, a vivid greenish-yellow dyed fabric was obtained. The fastness resistance of this dyed fabric was good. Also,
The elemental analysis values agreed well with the calculated values as shown in the table below.

[Table] Example 2 4.0g of the compound represented by the following formula, A mixture of 1.6 g of sodium carbonate, 2.5 g of dimethyl sulfate and 20 ml of dimethyl formamide was heated to 80° C. and kept warm for about 8 hours. After cooling to room temperature, the precipitated crystals were collected by discharging into 100 ml of water, washing and drying to obtain 4.0 g of a compound represented by the following structural formula. When polyester fiber was dyed at high temperature (130°C) using this dye, a vivid greenish-yellow dyed fabric was obtained. The light fastness of this dyed fabric was good. The elemental analysis values agreed well with the calculated values as shown in the table below.

[Table] Example 3 3.4g of the compound represented by the following formula, 1.6g sodium carbonate, n-octyl bromide
A mixture of 3.8g and 20ml dimethylformamide
It was heated to 80°C and kept warm for about 8 hours. After cooling to room temperature, the precipitated crystals were collected by discharging into 100 ml of water, washed, and dried to obtain 4.4 g of a compound represented by the following structural formula. When polyester fibers were dyed at high temperature (130°C) using this dye, a vivid greenish-yellow dyed fabric was obtained. The light fastness of this dyed fabric was good. Furthermore, the elemental analysis values were in good agreement with the calculated values as shown in the table below.

[Table] Example 4 4.1g of the compound represented by the following formula, Potassium carbonate 2.1g, p-toluenesulfonic acid-
A mixture of 4.6 g of γ-methoxypropyl ester and 20 ml of N-methylpyrrolidone was heated to 100°C,
It was kept warm for about 8 hours. Then, after cooling to room temperature, add water
The precipitated crystals were collected by discharging into 100 ml, washed and dried to obtain 4.6 g of a compound represented by the following structural formula. When polyester fiber was dyed at high temperature (130°C) using this dye, a vivid greenish-yellow dyed fabric was obtained. The light fastness of this dyed fabric was good. Furthermore, the elemental analysis values were in good agreement with the calculated values as shown in the table below.

[Table] Example 5 3.4g of the compound represented by the following formula, A mixture of 1.6 g of sodium carbonate, 3.8 g of 2-ethylhexyl bromide and 17 ml of dimethylformamide was heated to 80° C. and kept warm for about 8 hours. After cooling to room temperature, the precipitated crystals were collected by discharging into 100 ml of water, washed, and dried to obtain 4.3 g of a compound represented by the following structural formula. When polyester fiber was dyed at high temperature (130°C) using this dye, a vivid greenish-yellow dyed fabric was obtained. The light fastness of this dyed fabric was good. Furthermore, the elemental analysis values were in good agreement with the calculated values as shown in the table below.

[Table] Example 6 The dyes shown in Table 1 were synthesized by the same method as in Example 1. These dyes were used to dye polyester fibers at high temperature (130°C). The color tone of the obtained dyed fabric was as shown in the right column of Table 1 below. In addition, X and

The number before the substituent in the substituent column of [Formula] indicates the substitution position in the benzene nucleus.

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Claims (1)

[Claims] 1. General formula [] (wherein, Aminosulfonyl group, alkylsulfonyloxy group, alkenylsulfonyloxy group, arylsulfonyloxy group, alkylaminosulfonyloxy group, alkenylaminosulfonyloxy group, arylaminosulfonyloxy group, cycloalkylaminocarbonyl group, arylthiocarbonyl group or alkylthiocarbonyl group [Formula] represents a benzene nucleus optionally substituted with a chlorine atom, a bromine atom, or a lower alkyl group.) A compound represented by the general formula [] D-SO ₃ R ¹ ......[ ] (In the formula, D represents an optionally substituted phenyl group, and R ¹ is an alkyl group having 1 to 12 carbon atoms, a hydroxy lower alkyl group, a lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower alkyl group) group, lower alkoxycarbonyl lower alkyl group, acyloxy lower alkyl group,
Aryloxy lower alkyl group, cyano lower alkyl group, lower alkylamino lower alkyl group, halogeno lower alkyl group, cycloalkyl group, aralkyl group, phenyl group which may have a substituent or 2 to 4 carbon atoms Indicates an alkenyl group having ) A compound represented by the general formula [] R ¹ −Z ......[] (wherein R ¹ has the same meaning as in the above general formula [], and Z represents a halogen atom.) or a compound represented by the general formula [ ] (R ² ) ₂ SO ₄ ......[] (wherein R ² represents a lower alkyl group). ] (In the formula, X, R ¹ and [Formula] have the same meanings as in the general formulas [ ], [ ] and [ ].) A method for producing a pyridone-based azo dye represented by the following.